Method for Applying a Polymeric Film to a Substrate and Resulting Articles

ABSTRACT

A polymeric film assembly comprising a first solidified interlayer on a polymeric film or laminate comprising the same that is contacted with at least a portion of a surface of an underlying article to provide, for example, desired surface characteristics. At least a portion of the first solidified interlayer becomes a softened interlayer positioned between the polymeric film and the surface of the article when contacted as such. The softened interlayer is then converted to a second solidified interlayer, which second solidified interlayer may be in a different form than or same form as the first solidified interlayer initially provided, for adherence of the polymeric film to at least the portion of the surface of the article. Ease of removal and/or repair of polymeric film and laminates comprising the polymeric film that are so applied is facilitated.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority from U.S. Provisional PatentApplication No. 62/577,960 filed on Oct. 27, 2017, which is incorporatedby reference herein in its entirety.

BACKGROUND OF THE INVENTION

The present invention is directed toward a method for applying apolymeric film to a substrate and resulting articles.

Polymeric materials (also referred to herein simply as “polymers”) areused in many applications, often in the form of a film. A “film” isgenerally understood to be a relatively thin, continuous, single layerof material. In contrast, many conventionally applied “coatings” do notform a continuous or uniform layer of material on an underlyingsubstrate. As such, unlike polymeric films, coatings are often not ableto be physically separated from the supporting substrate on which theyare formed so that they can be used as a stand-alone layer or as one ofmultiple layers in another application. Thus, coating technology has itslimitations and is generally differentiated from that associated withpolymeric films.

Polymeric films are often capable of imparting desired properties intheir intended application without the need for coating multiple layersor laminating multiple films together and are widely used in manyapplications. Whether a polymeric film is suitable for an intendedapplication depends upon, for example, its physical properties such asstrength, elasticity, clarity, color, durability, and the like. Evenwhen properties of a polymeric film are optimized, however, thosebenefits are often not fully realized due to conventional methodologyfor applying such films to an underlying surface, which methodologyoften results in entrapment of air—visible as a defect—between thepolymeric film and underlying surface. This problem, and one solutiontherefor, is described in U.S. Patent Publication No.US-2015-0183198-A1.

As described in U.S. Patent Publication No. US-2015-0183198-A1, paintedsurfaces are commonly used in many different types of applications.Painted surfaces may not only improve aesthetic properties, but they mayalso or alternatively improve functional properties of underlyingsurfaces and help protect the same. One such application is in thetransportation industry, where exterior painted surfaces are typicallyexposed to a variety of environments, some of which can be very harsh onthe surface. Examples of articles in the transportation industry havingsuch painted surfaces include vehicles providing transportation overland, in the water, and in the air. Such vehicles include aircraft andland-based motorized vehicles like automobiles and trucks. The paint onsuch surfaces can function to protect the underlying surface from damagedue to that exposure. However, the paint itself must also be durable towithstand repeated exposure to such damaging environments.

Recently, paint in film form has been developed for application to suchsurfaces as an alternative to traditional paint, which traditional paintis typically liquid-based and applied to surfaces in its liquid form.Paint in film form is based on at least one polymeric film and is alsoreferred to herein as a “polymeric film” or “polymeric paint film.” Anexample of such polymeric paint film is described in U.S. PatentPublication No. US-2010-0059167-A1, entitled “Paint Replacement Films,Composites Therefrom, and Related Methods.”

Yet, as with application of other polymeric films to surfaces,particularly those surfaces having complex topographies, adequateadhesion at an interface and effective removal of entrapped air betweenthe polymeric film and the underlying surface has proven to be achallenge. For example, in many cases, when adhesive adhering apolymeric film attaches to an underlying surface, which adherence doesnot necessarily progress along a uniform front, particularly astopography of the underlying surface increases in complexity (i.e., suchthat it contains significant convex and concave portions), air oftenbecomes entrapped at the interface between the polymeric film and theunderlying surface. Due to the adhesive's presence at the advancingfront, beyond which is entrapped air, air becomes increasingly difficultto completely remove as adherence of the polymeric film progresses. Assuch, mechanisms for facilitating air bleed from such interfaces havebeen explored.

Many conventional air bleed mechanisms rely on use of structuredadhesive layers to remove entrapped air. For example, see U.S. PatentPublication No. 2011/0111157 and U.S. Pat. No. 7,332,205. Anotherpolymeric film-based structure known to facilitate air bleed between thestructure and an underlying surface after application includes amicrostructured surface, such as that described in U.S. Pat. No.5,897,930. While effective in many applications, such microstructureshave been found to obscure optical clarity in certain applications. Forexample, structure from the adhesive layer is often still visible(including to the naked human eye) after application of the polymericfilm to an underlying surface. Visibility is even more pronounced asthickness of the polymeric film decreases and/or transparency of thepolymeric film increases. As is readily understood, this presents a lessthan ideal solution to the problem of removal of entrapped air. Inaddition, types of polymeric films able to be effectively applied to anarticle's surface are limited by the constraints associated withpresence of such a microstructured surface.

Optical clarity of polymeric materials is an important considerationwhen selecting materials for use in optical and other applications wherespecific surface aesthetics, relating to outward appearance of apolymeric film applied to an article, can be desirable. Surfaceaesthetics may alternatively or also relate to preservation orenhancement of properties of an underlying surface of the article towhich a polymeric film is applied. When the surface underlying anapplied polymeric film comprises a composite material, the presence ofentrapped air and other defects inherent within the underlying surfaceis more prevalent, yet the underlying surface is often more susceptibleto damage when attempting to preserve or enhance aesthetics of the same.

In the case of composite materials (e.g., a fiber-reinforcedcomposites), obtaining desired surface aesthetics without affectingphysical properties of the composite material surface often presentschallenges, which are increasing in importance given that compositematerials are finding increased use in applications where lightweightmaterials are desired and where an associated compromise in strength orstiffness of the material would likely be problematic. Many compositematerials are also useful in applications where corrosion resistance isdesired, as composite materials more often exhibit excellent corrosionresistance as compared to alternative materials.

A wide variety of composite materials are known. In the case of afiber-reinforced composite, a polymeric resin matrix and fibrousreinforcement together often form the composite. A variety of materialscan be used for each of the polymeric resin matrix and the fibrousreinforcement components. For example, materials useful for fibrousreinforcement include carbon fibers, boron fibers, and glass fibers.Further, examples of materials useful for the polymeric resin matrixinclude thermoplastics (e.g., nylon) and thermosets (e.g., epoxies andphenolics).

Due to their beneficial properties, a variety of specialized sportingimplements and other articles are increasingly being made from compositematerials. For example, composite materials are increasingly being usedin shaft-based sporting implements (i.e., those sporting implementshaving a generally elongated portion, which may or may not be hollow oruniform in thickness and shape throughout) and similar articles. Sucharticles include, for example, golf clubs, bicycle frames, hockeysticks, lacrosse sticks, skis, ski poles, fishing rods, tennis rackets,arrows, polo mallets, and bats. As an example, the use of compositematerials enables golf club manufacturers to produce shafts havingvarying degrees of strength, flexibility, and torsional stiffness.

In addition, a variety of articles in the transportation and energyindustries are increasingly being made from composite materials. Forexample, composite materials are often used to make various aerospacecomponents, such as wing and blade components, including those onhelicopters and specialized military aircraft. Further, compositematerials are often used to make various automotive components, bothinterior and exterior, including body panels, roofs, doors, gear shiftknobs, seat frames, steering wheels, and others. In the energy industry,composite materials are used to make wind mill blades—e.g., large windturbine blades are made more efficient through the use of carbonfiber-reinforced composites. Indeed, the number of current and potentialapplications for composite materials is extensive.

Beneficially, composite materials offer enhancements in strength,stiffness, corrosion resistance, and weight savings. These beneficialproperties are often balanced against competing relative weaknesses inabrasion resistance and impact resistance. In addition, as manycomposite articles are made by layering multiple, individual compositematerial layers to achieve the desired properties, such compositearticles are susceptible to interlayer delamination, particularly uponimpact. This is especially the case with carbon fiber-reinforcedcomposites (also referred to as “CFR composites”). When interlayerdelamination occurs, structural integrity of such articles iscompromised, sometimes leaving the composite article useless asintended. Further, in extreme cases where the composite articlefractures, a sharp broken surface can result (i.e., with reinforcingfibers extending haphazardly therefrom), which impacts not only theusefulness of the article, but also the safety of those using sucharticles and those around them. Thus, breakage prevention andcontainment are also important design factors.

In order to enhance certain properties of composite articles, gel coatsor similar protective coatings have conventionally been used. Gel coatsoften impart a glossy appearance and improve other aesthetic propertiesof the article. In addition, gel coats can provide some, althoughlimited, enhancements in abrasion resistance. Gel coats or similarprotective coatings are conventionally applied to composite articlesthat are formed by molding for, if no other reason, aestheticenhancement. Particularly when molding articles from compositematerials, however, surface imperfections are likely to develop, givingrise to a need for aesthetic enhancement. One mechanism for theincreased number of surface imperfections in molded composite articlesis associated with tiny air bubbles forming at the interface with themold when the polymer matrix of such composites does not sufficientlyflow throughout the reinforcement (e.g., fibers) during molding. Theresult is that the surface of the composite article, which is formedagainst the face of the mold, contains imperfections such as voids thatcan detract from a glass-like or otherwise desired appearance.Imperfections can complicate the process of finishing the surface of thecomposite article.

There are two widely used methods of applying gel coats or similarexterior protective coatings to composite articles. The first methodinvolves spraying the gel coat onto an exterior surface of a compositearticle after the article is formed (e.g., by molding). Imperfectionscan complicate the process of finishing the surface of a compositearticle according to this method. For example, air can become entrappedwithin voids on the surface when a coating is spray-applied on thesurface. At such locations of entrapped air, a coating has no substrateto adhere to. Hence, the coating will typically either flow into thevoid or de-wet that area on the surface. In addition to complicationsassociated with entrapped air, conventional coatings flowing over asurface in general tend to result in a replicated underlying surfacetexture on the outwardly exposed surface of the hardened coating afterit conforms to undulations and imperfections in the underlying surface.

The second method involves eliminating this subsequent processing (e.g.,post-molding) step by pre-applying the gel coat to the interior surfaceof, for example, a mold where it can then be transferred to an exteriorsurface of the composite article formed therein. For example, see U.S.Pat. Nos. 4,081,578; 4,748,192; and 5,849,168. This method, which is onevariation of “in-mold processing,” is sometimes referred to as in-molddecoration or in-mold labeling depending on the application andmaterials used. Another variation in the use of in-mold processing forapplication of materials, although complicated and inefficient, isdescribed in U.S. Pat. No. 5,768,285.

When a polymeric film, as compared to a coating, is applied to asurface, complications still exist. For example, the process forconventional application of a pressure-sensitive adhesive (PSA)-backedpolymeric film can also be complicated by voids. Similar tocomplications associated with application of a conventional coating, atlocations of entrapped air on a surface, a polymeric film and anyadhesive backing thereon have no substrate to adhere to. As such, andgiven that the polymeric film is not a liquid coating, a polymeric filmcannot flow into the void or dewet the surface. As a result, thepolymeric film generally will span the void with air trapped underneath.If pressure is applied to such areas, and if the polymeric film hassufficient stretchability, the polymeric film will generally stretchinto the space of the void, which creates visual imperfections on thesurface. If entrapped air is not removed, during use of the resultingarticle, the entrapped air will often expand or contract, which processcreates protrusions or depressions within the polymeric film's surface.In addition to complications associated with entrapped air, conventionalpolymeric films often have a fixed thickness, which factor translatesinto replication of an underlying surface texture on the outwardlyexposed surface of the film as it conforms to undulations andimperfections in the underlying surface.

All things considered, alternative methodology for application ofpolymeric films to surfaces of articles is desired. Such a need isparticularly illustrated in conjunction with use of conventionalspray-applied clear coats, which methodology generally requiresapplication of several coating layers, often with sanding in betweeneach coat, in order to obtain a smooth surface with desired glosscharacteristics. Particularly when the underlying surface is afiber-based composite material, this process is not only time consuming,but can also damage the fiber-based surface during sanding.

SUMMARY OF THE INVENTION

According to the invention, a polymeric film or laminate comprising thesame is applied to at least a portion of a surface of an underlyingarticle to provide, for example, desired surface characteristics. Toassist in such application, a first solidified interlayer is appliedonto the surface of the polymeric film or laminate comprising thepolymeric film to form a polymeric film assembly to be contacted withthe portion of the surface of the article. The polymeric assembly isapplied to at least a portion of the surface of the article bycontacting the first solidified interlayer to the surface of the articlesuch that at least a portion of the first solidified interlayer becomesa softened interlayer positioned between the polymeric film and thesurface of the article. The softened interlayer is then converted to asecond solidified interlayer, which second solidified interlayer may bein a different form than or same form as the first solidified interlayerinitially provided, for adherence of the polymeric film to at least theportion of the surface of the article.

Ease of removal and/or repair of polymeric film and laminates comprisingthe polymeric film that are so applied is facilitated as the polymericfilm and layers adjacent the second solidified interlayer can beefficiently and effectively separated from the underlying article,leaving behind a substantial portion of the second solidified interlayeron the underlying article. Without the need to utilize additionalsolidified interlayer material in associated methodology, anotherpolymeric film or a laminate comprising the same can be efficiently andeffectively applied to that surface of the article according toconventional methodology.

DETAILED DESCRIPTION OF THE INVENTION

According to the invention, a polymeric film assembly comprising apolymeric film is applied to at least a portion of a surface of anunderlying article. In that regard, a polymeric film having desiredsurface characteristics (e.g., smoothness, gloss, etc.) is applied to anunderlying surface of the article.

In order to assist in application of such a polymeric film to anunderlying surface, particularly a fiber-based composite materialsurface (i.e., fiber-based surface) of an article, a roomtemperature-solidified interlayer (also referred to herein as a“solidified interlayer”) is present on the surface of the polymeric filmassembly to be contacted with the surface of the article to which thepolymeric film is applied. When the polymeric film assembly is appliedto a heated surface of an article, only the heated portion of thesolidified interlayer softens to the form of a “softened interlayer.”Upon application of a polymeric film assembly to an underlying surfaceas such, the softened interlayer exhibits a viscosity so that it canflow over and into voids and defects that are commonplace withinfiber-based surfaces, which flow translates into a smoother surface onthe resulting article and such a surface with fewer visible defects.Advantageously, according to this exemplary embodiment, flow of thesoftened interlayer from the interface of the polymeric film assemblyand underlying substrate with which it is contacted is minimized as onlythe portion of solidified interlayer in contact with the heated surfacebecomes softened.

After contact of the softened interlayer with the underlying surface,the softened interlayer than returns to a solidified interlayer,optionally with polymerization of the same. As used herein, the term“polymerization” and the like encompasses what is sometimes referred toby those of ordinary skill in the art as “cure,” “curing,” and the like.Those terms may be used interchangeably herein and by those of ordinaryskill in the art. For example, use of the term curing is oftenassociated with polymerization (aka “cure”) of epoxy resins.

According to one embodiment, after application to the surface, thesoftened interlayer reverts to essentially the same—in terms ofchemistry and material properties—solidified interlayer upon cooling.According to another embodiment, after application to the surface, asoftened interlayer of polymerizable composition partially polymerizesand also further solidifies by cooling. Upon cooling, the previouslysoftened interlayer can exhibit properties associated with aviscoelastic fluid, a viscoelastic solid, or an elastic solid. In anexemplary embodiment, after application of the polymeric film to theunderlying surface and cooling to room temperature, the solidifiedinterlayer exhibits a room temperature Brookfield viscosity of greaterthan about 20,000 centiPoise.

Using methodology of the present invention, polymeric films of theinvention impart desired surface characteristics as an improvement overconventional techniques using a surface coating that is spray-applied orotherwise. Resulting articles having improved surface characteristicsare, thus, obtainable using methodology of the invention. In preferredembodiments, resulting articles have at least comparable, and oftensuperior, surface characteristics as compared to those includingtraditionally spray-applied clear coatings and those polymeric filmsadhered to an underlying surface using conventional methodology.

Another advantage of the present invention relates to ease of removaland/or repair of polymeric film applied to underlying surfaces accordingto improved methodology. For example, in one embodiment, the solidifiedinterlayer adheres better to the underlying surface than to thepolymeric film and/or layers (e.g., optional adhesive layer) adjacentthereto when the polymeric film is part of a laminate comprising thesame. Lack of covalent crosslinking between the solidified interlayerand polymeric film and/or layers adjacent thereto contributes to thisdifferential adherence. Without such covalent crosslinking, thepolymeric film and layers adjacent thereto can be efficiently andeffectively separated from the underlying article, leaving behind asubstantial portion of the solidified interlayer on the underlyingarticle.

Without the need to utilize additional interlayer material in associatedmethodology, polymeric film or laminates comprising the same can beefficiently and effectively reapplied to that surface of the articleaccording to conventional methodology. Surface voids and defects thatwere present on the underlying surface of the article, such as is oftenthe case with fiber-based surfaces, before application of the removedpolymeric film according to methodology of the invention remainsubstantially obviated by the solidified interlayer remaining on thesurface as a result of its application during the original polymericfilm application.

Polymeric Film and Laminates Comprising the Polymeric Film

“Polymeric films” of the invention are relatively thin, continuous,single layers of polymeric material. Polymeric films of the inventionare not generally considered by those of ordinary skill in the polymerarts to be adhesives.

In further embodiments, more than one polymeric film or other layers ofmaterial may be provided in the form of a “laminate” for application toan article's surface. Although thickness may be much greater, accordingto one aspect of a polymeric film laminate, the laminate has an overallthickness of less than about 400 microns. In a further embodiment, thelaminate has an overall thickness of less than about 200 microns. In afurther embodiment still, the laminate has an overall thickness of lessthan about 50 microns. In yet a further embodiment, the laminate has anoverall thickness of about 10 microns. Generally, thicker laminatesprovide greater abrasion resistance, while thinner laminates may be usedwhen corrosion or similar resistance is of primary concern.

The nature of polymeric film laminates useful in the present inventionmay vary, depending for example on whether the laminate is beingfirst-applied to a surface of an article with a solidified interlayertherein contacting that surface or whether the laminate is being appliedto that same surface after removal of a polymeric film applied using thesolidified interlayer from that same surface. For example, in oneembodiment, a polymeric film laminate that is applied to the surface ofthe article from which a polymeric film assembly comprising a solidifiedinterlayer was applied previously includes an adhesive (e.g.,pressure-sensitive adhesive) layer. In an exemplary aspect of thisembodiment, such a polymeric film laminate comprises an adhesive layer,as opposed to a solidified interlayer, on the surface of the polymericfilm to be contacted with the underlying surface on which it is to beapplied.

A wide variety of polymeric films are known, sometimes being referred toas “protective sheets,” and which have been applied to a variety ofunderlying surfaces, including those based on composite materials. See,for example, U.S. Pat. No. 8,545,959, the contents of which areincorporated herein by reference. However, as discussed in thebackground above, methods for their application can be complicated,particularly given problems associated with removal of entrapped airbetween the polymeric film and underlying surface. Entrapped air is onefactor contributing to often visible defects in the resulting surface.

The polymeric film may, optionally, be at least partially pigmented(i.e., colored) and/or at least partially metallized as a “polymericpaint film.” In an exemplary embodiment, a polymeric film of theinvention is at least partially pigmented. Depending upon, among otherconsiderations, the type of pigment and thickness of the polymeric film,pigmented polymeric films of the invention may be substantiallytranslucent or substantially opaque.

In another exemplary embodiment, a polymeric film of the invention ismetallized. Generally, metallized polymeric films of the invention aresubstantially opaque, but metallized polymeric films may be at leastpartially transparent depending on the degree of metallization.

In a further exemplary embodiment, a polymeric film of the invention isboth pigmented and metallized. However, the polymeric film need notcontain additives altering the appearance of an underlying article to beconsidered a polymeric film applicable according to methods of theinvention.

In another exemplary embodiment, the polymeric film is essentially freeof pigment and metallization. According to one aspect of thisembodiment, the polymeric film is substantially transparent. Accordingto another aspect of this embodiment, the polymeric film issubstantially translucent. According to another aspect of thisembodiment, the polymeric film is substantially opaque.

In order to facilitate adherence of the polymeric film to surfaceshaving relatively complex topographies, preferably, the polymeric filmis stretchable. The term “stretchable” refers to a material's ductilityand its ability to be stretched (i.e., elongated). Exemplary stretchablepolymeric films are capable of being stretched to a length that is atleast about 105% of its initial length or more without breaking. Forexample, a stretchable polymeric film having a length of 100 centimetersis capable of being stretched to a length of 105 centimeters or morewithout breaking. In one embodiment, stretchable polymeric films arecapable of being stretched to a length that is at least about 125% ofits initial length or more without breaking. For example, a stretchablepolymeric film having a length of 100 centimeters is capable of beingstretched to a length of 125 centimeters or more without breaking. Inanother embodiment, stretchable polymeric films are capable of beingstretched to a length that is at least about 150% of its initial lengthor more without breaking. For example, a stretchable polymeric filmhaving a length of 100 centimeters is capable of being stretched to alength of 150 centimeters or more without breaking.

In one embodiment, the polymeric film does not fully recover oncestretched. An exemplary polymeric film having such reduced recovery iscapable of being stretched to a length that is at least about 110% ofits initial length without breaking, but the polymeric film does notrecover to its original state after such stretching. According to oneaspect of this embodiment, the polymeric film recovers to no less thanabout 105%, or preferably to no less than about 110% of its initiallength, after stretching to a length that is at least about 110% of itsinitial length.

In another embodiment, the polymeric film is not only stretchable, butalso extensible. The terms “extensible” and “extensibility” refer to amaterial's ductility and its ability to be stretched and recover toessentially its original state after stretching. Extensible polymericfilms are capable of recovering to their original state when stretchedup to about 125% of their initial length or more. That is, extensiblepolymeric films are capable of recovering to their original state whenstretched to a length that is about 125% or more of its initial length.For example, a polymeric film having an initial length of about 100centimeters is capable of recovering to a length of about 100centimeters after being stretched to a length of 125 centimeters or morewhen it is extensible. Preferably, extensible polymeric films arecapable of recovering to their original state when stretched up to about150% of their initial length or more.

In another preferred embodiment, the polymeric film exhibits essentiallyno plastic deformation when stretched up to about 125% of its initiallength—e.g., when a polymeric film is stretched from an initial lengthof 100 centimeters up to a length of about 125 centimeters. In a furtherpreferred embodiment, the polymeric film exhibits essentially no plasticdeformation when stretched up to about 150% of its initial length—e.g.,when a polymeric film is stretched from an initial length of 100centimeters up to a length of about 150 centimeters. Preferably, a forceof less than about 40 Newtons is required to elongate the polymeric filmto 150% its initial length.

According to a preferred embodiment of the invention, polymeric filmsare capable of elongating more than 200% before breaking. In stillanother preferred embodiment, the polymeric film exhibits greater thanabout 210% elongation at break when tested according to ASTM D638-95. Ina further preferred embodiment, the polymeric film exhibits greater thanabout 260% elongation at break when tested according to ASTM D638-95. Ina still further preferred embodiment, the polymeric film exhibitsgreater than about 300% elongation at break when tested according toASTM D638-95. In yet another preferred embodiment, the polymeric filmexhibits greater than about 350% elongation at break when testedaccording to ASTM D638-95.

Useful polymeric films comprise any suitable chemistry. While more thanone polymeric material can be used in polymeric films and other layerswithin laminates of the invention, the following description isgenerally made with reference to one such type of polymeric materialwithin that layer for simplicity only.

The polymeric film comprises any suitable polymeric material. Forexample, the polymeric film may be polyurethane-based,polyacrylate-based, polyepoxide-based, or polyester elastomer-based.Although generally not preferred for certain embodiments due to itsrelatively low extensibility, the polymeric film can also bepolyvinyl-based, such as polyvinyl chloride (PVC), polyvinyl acetate(PVA), polyvinylidene fluoride (PVDF), or general polyvinyl fluoride(PVF) (e.g., that available from DuPont under the TEDLAR tradedesignation), or α-olefin-based in embodiments where full recovery ofthe polymeric film after stretching is not necessary or desired.

The polymeric film is preferably polyurethane-based in that it comprisesany suitable polyurethane material. For simplicity, the term“polyurethane” is sometimes used herein to reference polymeric materialcontaining urethane (also known as carbamate) linkages in combinationwith urea linkages (i.e., in the case of poly(urethane-urea)s). Thus,polyurethanes of the invention contain at least urethane linkages and,optionally, urea linkages. Many commercially available polyurethanes areavailable and suitable for use as polyurethane-based polymeric filmsaccording to the invention. For example, suitable polyurethanes areavailable from entrotech, inc. (Columbus, Ohio) under the HT1331,HT2312, HT2313 trade designations.

In addition to additives altering the appearance of an article, whichadditives are present in exemplary embodiments, any suitable additivescan optionally be included in the polymeric film. For example,stabilizers (e.g., antioxidants, heat stabilizers, and UV-stabilizers),crosslinkers (e.g., aluminum or melamine crosslinkers), binders,corrosion inhibitors, plasticizers, photocrosslinkers, fillers, andother conventional additives as known to those of ordinary skill in theart can be incorporated into the polymeric film. If desired, an adhesionpromoter may be included in the polymeric film. However, in preferredembodiments, the material comprising the polymeric film is selected tobe chemically compatible with any adjacent layers within laminates ofwhich the polymeric film is a part. Thus, an adhesion promoter is notrequired according to preferred embodiments of the invention.

The polymeric film may be pigmented and/or metallized and substantiallytransparent, substantially translucent, or substantially opaque,depending on the application. When the polymeric film is substantiallytransparent or substantially translucent, but a pigmented and/ormetallized aesthetic is desired, at least one pigmented and/ormetallized layer may be provided within a laminate comprising thepolymeric film—e.g., between the polymeric film and an optional adhesivelayer or between the polymeric film and the solidified interlayer.Alternatively, or in combination with at least one pigmented and/ormetallized layer sandwiched between the polymeric film and an outerlayer on a first major side of a laminate comprising the polymeric film,a pigmented and/or metallized layer can be provided on the opposite sideof the polymeric film in another embodiment. When the polymeric film issubstantially opaque in such an embodiment, pigment and/or metallizationis generally provided on an outer surface of the polymeric film, on aside that is outwardly visible when the polymeric film is adhered to asurface. In this embodiment, the polymeric film can be impregnated witha material (e.g., titanium dioxide) that causes the polymeric film tofunction as a reflective background, enhancing color of the overlyingpigment. Pigment and/or metallization may also be provided on an outersurface of the polymeric film, alone or in combination with a pigmentedand/or metallized layer within a laminate comprising the polymeric film,when the polymeric film is substantially transparent or substantiallytransparent.

Those of ordinary skill in the art are readily familiar with materialsand methodology for formation of pigmented layers and metallized layers.Any suitable such material and methodology may be utilized in thoseembodiments of the present invention where the polymeric film ispigmented and/or metallized. While more than one pigmented and/ormetallized layer can be used in laminates comprising polymeric films ofthe invention, the following description is made with reference to onesuch layer for simplicity only. Recognize that, if multiple pigmentedand/or metallized layers are used, each pigmented and/or metallizedlayer within such a laminate can be the same or different.

When present, the metallized layer comprises any suitable material andprovides desired aesthetics when the laminate comprising the polymericfilm is adhered to a surface. The metallized layer can be a continuousor discontinuous layer. Note that the metallized layer may consistessentially of graphics, patterns, and the like, which results in thatlayer being a discontinuous layer and/or a non-planar layer.

In one embodiment, a metallized layer is formed by chemical or physicalvapor deposition of a thin layer of aluminum or a desired metal or alloythereof. The metallized layer comprises any suitable thickness. In anexemplary embodiment, the metallized layer has a maximum thickness ofabout 1,000 Angstroms, preferably less than about 500 Angstroms. In afurther embodiment, the metallized layer has a minimum thickness of atleast about 70 Angstroms.

When present, the pigmented layer comprises any suitable material andprovides desired aesthetics when a laminate comprising the polymericfilm is adhered to a surface. The pigmented layer can be a continuous ordiscontinuous layer. Note that the pigmented layer may consistessentially of graphics, patterns, and the like, which results in thatlayer being a discontinuous layer and/or a non-planar layer.

The pigmented layer generally comprises at least one material impartingdesired color to the laminate comprising the polymeric film or portionthereof. In one embodiment, the pigmented layer comprises dye. Inanother embodiment, the pigmented layer comprises ink. Any suitablecommercially available ink can be used. Non-limiting examples ofsuitable inks include pigmented acrylic ink (including pigmented,fast-dry, acrylic ink), pigmented urethane ink, epoxy ink, and aurethane enamel coating such as that sold by PRC-Desoto International,Inc. (a division of PPG Aerospace) of Glendale, Calif. under the tradedesignation, DESOTHANE HS.

Any suitable additives can optionally be used in the pigmented layer.For example, stabilizers (e.g., antioxidants, heat stabilizers, andUV-stabilizers), crosslinkers (e.g., aluminum or melamine crosslinkers),corrosion inhibitors, plasticizers, photocrosslinkers, additionalcolorants, fillers, and other conventional additives as known to thoseof ordinary skill in the art can be incorporated into the pigmentedlayer. If desired, an adhesion promoter may be included in the pigmentedlayer. However, in preferred embodiments, the material comprising thepigmented layer is selected to be chemically compatible with anyadjacent layers of laminates comprising the polymeric film. Thus, anadhesion promoter is not required according to preferred embodiments ofthe invention.

Preferably, the pigmented layer is essentially free of components thatmay tend to migrate to the outer surface of the polymeric film, alaminate comprising the polymeric film, or to an interface therein,where such components may promote interlayer delamination or otherwisedetrimentally affect the adherence of the polymeric film to adjacentsurfaces or layers. The pigmented layer is also preferably resistant tochemicals to which it may be exposed during use of the polymeric film.

The pigmented layer comprises any suitable thickness. In an exemplaryembodiment, the pigmented layer has a maximum thickness of about 50microns, more preferably less than about 25 microns, and preferablyabout 5 microns to about 8 microns.

Preferably, the polymeric film is essentially free of components thatmay tend to migrate to the outer surface of the polymeric film or to aninterface within laminates comprising the polymeric film, where suchcomponents may promote interlayer delamination or otherwisedetrimentally affect adherence of the polymeric film to adjacentsurfaces or layers. The polymeric film is also preferably resistant tochemicals to which it may be exposed during use of the polymeric film.For example, it is preferred that the polymeric film is resistant todegradation by water and hydraulic fluids. It is also preferred that thepolymer layer is thermally resistant to temperatures to which it may beexposed during use of the polymeric film.

The polymeric film comprises any suitable thickness. In one embodiment,the polymer layer has a thickness of about 10 microns to about 400microns. In another embodiment, the polymeric film has a thickness ofabout 10 microns to about 200 microns. In yet another embodiment, thepolymeric film has a thickness of about 10 microns to about 50 microns.In an exemplary embodiment, the polymeric film is about 25 microns thickor less. It has been found that use of a relatively thin polymer layercontributes to superior stretchability of the polymeric film. Suchstretchability allows polymeric films of the invention to be effectivelyused in covering articles having curved or other non-planar surfaces.

When present in laminates comprising the polymeric film, the adhesivelayer comprises any suitable material. According to one embodiment, theadhesive layer generally comprises a base polymer with one or moreadditives. While any suitable chemistry can be used for the base polymerin the adhesive layer, (meth)acrylate (i.e., acrylate and methacrylate)chemistry is preferred. In particular, an adhesive based on 2-ethylhexyl acrylate, vinyl acetate, and acrylic acid monomers polymerized asknown to those skilled in the art can be used as the base polymer.However, other suitable chemistries are known to those skilled in theart and include, for example, those based on synthetic and naturalrubbers, polybutadiene and copolymers thereof, polyisoprene andcopolymers thereof, and silicones (e.g., polydimethylsiloxane andpolymethylphenylsiloxane). In a preferred embodiment, the adhesive layercomprises a pressure-sensitive adhesive (PSA).

Any suitable additives can optionally be used in conjunction with thebase polymer in the adhesive layer. For example, stabilizers (e.g.,antioxidants, heat stabilizers, and UV-stabilizers), crosslinkers (e.g.,aluminum or melamine crosslinkers), corrosion inhibitors, tackifiers,plasticizers, photocrosslinkers, fillers, and other conventionaladhesive additives as known to those of ordinary skill in the art can beincorporated into the adhesive layer. If desired, an adhesion promotermay be included in the adhesive layer. However, in preferredembodiments, the material comprising the adhesive layer is selected tobe chemically compatible with the polymeric film. Thus, an adhesionpromoter is not required according to preferred embodiments of theinvention.

Similar to the polymeric film, the adhesive layer may be pigmentedand/or metallized and substantially transparent, substantiallytranslucent, or substantially opaque, depending on the application anddepending on such properties of the polymeric film and any pigmentedand/or metallized layer within laminates comprising the polymeric film.In one embodiment, when the polymeric film is substantially transparentor substantially translucent, pigment and/or metallization is providedon the adhesive layer at its interface with the polymeric film. In thisembodiment, the adhesive layer can be impregnated with a material (e.g.,titanium dioxide) that causes the adhesive layer to function as areflective background, bringing out the color of the overlying pigment.

Preferably, the adhesive layer is essentially free of components thatmay tend to migrate to the outer surface of the polymeric film or to aninterface within a laminate comprising the polymeric film, where suchcomponents may promote interlayer delamination or otherwisedetrimentally affect adherence of the polymeric film to adjacentsurfaces or layers. The adhesive layer is also preferably resistant tochemicals to which it may be exposed during use of the polymeric film.For example, it is preferred that the adhesive layer is resistant todegradation by water and hydraulic fluids.

The adhesive layer comprises any suitable thickness. In one embodiment,the adhesive layer has a thickness of about 5 microns to about 150microns. In a further embodiment, the adhesive layer has a thickness ofabout 30 microns to about 100 microns. In an exemplary embodiment, theadhesive layer is about 25 microns thick or less. However, the thicknessof the adhesive layer can vary substantially without departing from thespirit and scope of the invention.

In an exemplary embodiment, a laminate comprising the polymeric film isa multi-layer extensible protective sheet as described in U.S. PatentPublication No. US-2008-0286576-A1, entitled “Protective Sheets,Articles, and Methods,” incorporated herein by reference in itsentirety. Another such exemplary laminate is described in U.S. PatentPublication No. US-2010-0059167-A1, entitled “Paint Replacement Films,Composites Therefrom, and Related Methods,” incorporated herein byreference in its entirety.

Until the polymeric film is adhered to a surface, it can be stored withan optional release liner adjacent the adhesive layer, when present. Theselection and use of such liners is within the knowledge of one ofordinary skill in the art. Advantageously, when employing improvedapplication methods according to the invention, the release liner towhich the adhesive layer is adhered need not be textured to impart airegress channels in the adhesive layer. In a preferred embodiment, whilesome randomly oriented texture may be present on the surface of theadhesive layer to be applied to an article, the adhesive layer isessentially free of ordered texture—e.g. air egress channels (such asthose present in structured release liners marketed by Loparex LLC ofCary, N.C., under the trade designation, POLY SLIK air releaseliners)—when a laminate comprising the polymeric film is adhered to asurface. As such, any release liner adhered to the adhesive layer priorto application of the laminate is essentially smooth according to suchpreferred embodiments.

Preferably, essentially smooth release liners have a profile roughnessparameter (R_(a)) value of less than about 50 nanometers as measuredaccording to, for example, DIN 4768. More preferably, essentially smoothrelease liners have a profile roughness parameter (R_(a)) value of lessthan about 30 nanometers as measured according to, for example, DIN4768. Even more preferably, essentially smooth release liners have aprofile roughness parameter (R_(a)) value of less than about 10nanometers as measured according to, for example, DIN 4768.

Those of ordinary skill in the art are readily familiar with the widevariety of suitable smooth release liners, many of which are readilymarketed as “optically clear” release liners. Exemplary release linersthat are essentially smooth include those marketed by the NORTON filmsgroup of Saint-Gobain Performance Plastics Corp. (Aurora, Ohio) underthe trade designations, OPTILINER and SUPRALINER.

Polymeric films can be applied to a variety of articles to formassemblies according to methodology of the present invention. Whenapplied to an article, the polymeric film and at least one exteriorsurface of the article are contacted with a polymerizable compositiontherebetween to form an assembly.

Interlayer

By use of the term “interlayer,” it is to be understood that such alayer is positioned between the polymeric film or laminate comprisingthe polymeric film and the underlying surface in resulting articlesafter application of the polymeric film according to methodology of theinvention. Before application of the polymeric film or laminatecomprising the polymeric film to the underlying surface, however,interlayer is also used to denote that layer of material in the absenceof surrounding structure. In that absence, the interlayer is outwardlyexposed, not being sandwiched between the polymeric film and theunderlying surface of the article onto which the polymeric film assemblyis to be contacted. Any suitable material can be used for interlayersaccording to the invention.

Understand that, before application to the underlying surface, asolidified interlayer may be fully polymerized, partially polymerized,or essentially non-polymerized. Preferably, after application of heat tothe same, the resulting softened interlayer has a relatively lowviscosity so that it can flow over and into voids and defects that arecommonplace within fiber-based surfaces, which flow translates into asmoother surface on the resulting article and such a surface with fewervisible defects. As measured, the softened interlayer may exhibit thedesired viscosity at room temperature or upon heating. Viscositymeasurements indicated herein are of the interlayer in its neat form(i.e., 100% non-volatile), without the presence of viscosity-reducingsolvents. Viscosity is measurable according to techniques well known tothose of ordinary skill in the art and may be measured using, forexample, a Brookfield rotational viscometer such as those available fromCole-Parmer (Vernon Hills, Ill.).

According to the invention, the interlayer exhibits a desired viscosityonly after heating to the softened interlayer. According to an exemplaryaspect of this embodiment, Brookfield viscosity of the interlayer isless than about 10,000 centiPoise after heating to form the softenedinterlayer. In another embodiment, Brookfield viscosity of theinterlayer is less than about 5,000 centiPoise after heating to form thesoftened interlayer. In yet another embodiment, Brookfield viscosity ofthe interlayer is less than about 2,000 centiPoise after heating to formthe softened interlayer. In still a further embodiment, Brookfieldviscosity of the interlayer is less than about 1,500 centiPoise afterheating to form the softened interlayer. In an exemplary embodiment,Brookfield viscosity of the interlayer is about 50 centiPoise to about1,500 centiPoise after heating to form the softened interlayer. Inanother exemplary embodiment, Brookfield viscosity of the interlayer isabout 400 centiPoise to about 1,500 centiPoise after heating to form thesoftened interlayer.

Any suitable composition and method for solidifying the same can be usedfor the interlayer according to methodology of the invention. Theinterlayer can comprise thermoplastic or thermoset polymers. As athermoplastic resin, the following are exemplary resins: polyamideresin, saturated polyester resin, polycarbonate resin, ABS resin,polyvinyl chloride resin, polyacetal resin, polystyrene resin,polyethylene resin, polyvinyl acetate resin, AS resin, methacrylateresin, polypropylene resin, and fluorine resin. Although chemistry canvary, epoxy, (meth)acrylate, and urethane-based compositions areparticularly well-suited and preferred for many applications.

In one embodiment, the softened interlayer is polymerizable using freeradical or similar polymerization methods. According to this embodiment,the softened interlayer and previously solidified interlayer from whichit results include at least one monomer (e.g., vinyl or (meth)acrylate).The at least one monomer can react with itself and, in some furtherembodiments, other monomers present. Depending on the type of radiationused, at least one initiator may also be included with the at least onemonomer in the softened interlayer and previously solidified interlayerfrom which it results.

In yet another embodiment, the softened interlayer is polymerizableusing cationic or similar polymerizable methods. According to thisembodiment, the softened interlayer and previously solidified interlayerfrom which it results include at least one monomer and at least onecationic initiator.

Polymerizable systems relying on ultraviolet, e-beam, or thermalpolymerization can be used. Such systems include, for example, one-partand two-part epoxy resins. Thermosetting resins and thermoplastic resinscan be used singly or in combination as an initial epoxy resin. The mostcommon epoxy resin types include those based on diglycidyl ether ofBisphenol A and the epoxy novolacs (comprised of glycidyl ethers ofcresol novolac, phenolic novolac, or Bisphenol A novolac). In oneembodiment, the present invention provides for use of lower viscosityepoxy resins, such as those based on the diglycidyl ether of BisphenolF. As compared to a typical epoxy resin based on diglycidyl ether ofBisphenol A (i.e., EPON 826 available from Resolution PerformanceProducts of Houston, Tex.), exemplary lower viscosity epoxy resins ofthe present invention (i.e., EPON 862 and EPON 863 also available fromResolution Performance Products), which are based on diglycidyl ether ofBisphenol F, are reported to have a viscosity of 2.5-4.5 Pa·s (25-45Poise) as compared to 6.5-9.6 Pa·s (65-96 Poise) when tested at 25° C.Another example of a Bisphenol F-derived epoxy resin is EPALLOY 8230,available from CVC Specialty Chemicals, Inc. of Moorestown, N.J. Thereported viscosity of EPALLOY 8230 epoxy resin is 2.5-4.7 Pa·s(2,500-4,700 centiPoise).

Generally, when a thermosetting resin is used, a curative is needed toeffectuate final cure of the resin, and any suitable curative can beused in that regard. As known to those skilled in the art, differentcuratives impart various advantages when used. For example, in epoxysystems, aliphatic amine curatives allow for room-temperature cure,whereas aromatic amines offer optimal chemical resistance and more rigidfinal parts. As another example, acid anhydride curatives can providesuperior electrical properties. It is to be understood, however, thatselection of the curative depends, among other well-known factors, oncuring conditions desired and the intended application. In an exemplaryembodiment, at least one curative is used that facilitates cure of theresin composition within about 45 to about 60 minutes when heated toabout 120° C. (250° F.).

An exemplary class of curatives useful for curing of epoxy resins is themodified aliphatic amine curatives such as those available from AirProducts and Chemicals, Inc. of Allentown, Pa. under the ANCAMINE tradedesignation. In that class, ANCAMINE 2441 curing agent is particularlyuseful in exemplary resins according to the invention.

Another class of curatives includes dicyandiamides, optionally with theuse of common accelerators. For example, a useful combination is OMICUREDDA 5, an ultra-micronized grade of dicyandiamide, and OMICURE U-52, anaromatic substituted urea used as an accelerator for dicyandiamide cureof epoxies (both available from CVC Specialty Chemicals, Inc. ofMoorestown, N.J.). Another useful combination is AMICURE CG-1400, amicronized grade of dicyandiamide, and AMICURE UR, a substitutedurea-based accelerator (1 phenyl 3,3 dimethyl urea) fordicyandiamide-cured epoxy resins (both available from Air Products andChemicals, Inc. of Allentown, Pa.).

Any suitable amount of the curative is used in resin compositions of theinvention. Generally, after the specific type of curative is selected,the amount used is calculated as is well known to those skilled in theart.

In another embodiment of a one-part system, after the polymeric film iscontacted with the underlying fiber-based surface, thermal radiation isused to initiate polymerization of the softened interlayer. Thermalradiation is supplied by heating the underlying fiber-based surfaceaccording to one aspect of the invention. Thermal radiation is suppliedby heating both the polymeric film assembly and underlying fiber-basedsurface according to another aspect of the invention. A latent curingagent is activated or a blocked reactive component (e.g., a blockedisocyanate) is unblocked upon initiation using thermal radiationaccording to exemplary aspects of this embodiment.

The type and amount of interlayer is selected according to theapplication and desired properties in the resulting article. In laminateform, where an adhesive layer is present on the surface of a laminatecomprising the polymeric film to be contacted with the underlyingsurface, the amount of interlayer applied thereto can be minimized to alevel that is sufficient to accommodate defects and fill in voids thatare present on the underlying surface. In the case of class A typesurfaces (e.g., as used in the automotive industry), where a primaryconcern is to eliminate entrapped air bubbles, only a small amount ofinterlayer is required. In certain embodiments, 1-5 grams per squaremeter (gsm) of interlayer is sufficient.

In alternate embodiments, where there is no existing adhesive layer, itis often preferable to maintain a minimum thickness of interlayer—andresulting solidified interlayer—between the polymeric film or laminatecomprising the same and the underlying substrate. According to oneaspect of that embodiment, the interlayer is selected such that theresulting solidified interlayer is about 5 to about 100 microns,preferably about 25 to about 50 microns, thick. If desired, optionalfiller material can be used to assist in maintaining that minimumthickness. An exemplary filler is 25-50 micron polymethylmethacrylate(PMMA) spheres manufactured by Sekisui Plastics Co., Ltd. under thetrade name TECHPOLYMER.

The length of time needed to adequately solidify the softened interlayercan vary. Preferably, the interlayer returns to a solidified interlayer(i.e., such that it is has a high enough viscosity to facilitateadequate adherence to the underlying surface—even though the overallcomposition may not be fully polymerized, if desired) in no more thanabout ten minutes, more preferably in no more than about five minutes,and even more preferably in no more than about one minute after contactof the softened interlayer with the underlying surface. Depending on theapplication and stage of processing, the interlayer can exhibitproperties associated with a viscoelastic fluid, a viscoelastic solid,or an elastic solid. In an exemplary embodiment, the solidifiedinterlayer exhibits a room temperature Brookfield viscosity of greaterthan about 20,000 centiPoise.

According to another aspect of an exemplary embodiment, when tested as astandalone film according to the Loss Factor Test Method describedbelow, a solidified interlayer exhibits a peak loss factor of less thanabout 1.0. It is to be understood that loss factor is often usedinterchangeably with the phrase “tan delta” and is understood to beessentially the same as “loss factor” described herein.

According to the Loss Factor Test Method, a dynamic mechanical analyzeravailable from TA Instruments (New Castle, Del.) under the tradedesignation, TA Instruments DMA Q800 is used to perform the test intension mode. Nominal sample sizes having a length of 5-12 mm, a widthof 4-8 mm, and a thickness of 0.02-0.2 mm can be used. A frequency of 1Hz, strain of 0.3%, and ramp rate of 3° C./minute can be used to measurevalues for determination of the loss factor of a sample. Such a lossfactor corresponds to the storage modulus of the composition beinggreater than its loss modulus. Storage modulus can also be tested usingthe dynamic mechanical analyzer described in conjunction with the LossFactor Test Method above.

Various modifications and alterations of the invention will becomeapparent to those skilled in the art without departing from the spiritand scope of the invention, which is defined by the accompanying claims.It should be noted that steps recited in any method claims below do notnecessarily need to be performed in the order that they are recited.Those of ordinary skill in the art will recognize variations inperforming the steps from the order in which they are recited. Inaddition, the lack of mention or discussion of a feature, step, orcomponent provides the basis for claims where the absent feature orcomponent is excluded by way of a proviso or similar claim language.Further, as used throughout, ranges may be used as shorthand fordescribing each and every value that is within the range. Any valuewithin the range can be selected as the terminus of the range.Similarly, any discrete value within the range can be selected as theminimum or maximum value recited in describing and claiming features ofthe invention. In addition, as discussed herein it is again noted thatthe polymerizable composition described herein may comprise allcomponents in one or multiple parts. Other variations are recognizableto those of ordinary skill in the art.

1. A method for applying a polymeric film to at least a portion of asurface of an article, the method comprising steps of: providing thepolymeric film or a laminate comprising the polymeric film; applying afirst solidified interlayer to a surface of the polymeric film or asurface of the laminate comprising the polymeric film to form apolymeric film assembly to be contacted with the portion of the surfaceof the article; heating at least a portion of the surface of the articleto form a heated surface; applying the polymeric film assembly to atleast a portion of the heated surface of the article by contacting thefirst solidified interlayer to the portion of the heated surface of thearticle such that at least a portion of the first solidified interlayerbecomes a softened interlayer positioned between the polymeric film andthe portion of the heated surface of the article; and converting thesoftened interlayer to a second solidified interlayer, which secondsolidified interlayer may be in a different form than or same form asthe first solidified interlayer initially provided, for adherence of thepolymeric film to at least the portion of the surface of the article,wherein the step of converting the softened interlayer to a secondsolidified interlayer comprises at least partial polymerization of thesoftened interlayer.
 2. The method of claim 1, wherein the polymericfilm is polyurethane-based.
 3. The method of claim 1, wherein theportion of the surface of the article is fiber-based.
 4. The method ofclaim 1, wherein Brookfield viscosity of the softened interlayer ismeasured using a Brookfield rotational viscometer to be less than about10,000 centiPoise.
 5. The method of claim 1, wherein Brookfieldviscosity of the softened interlayer is measured using a Brookfieldrotational viscometer to be less than about 5,000 centiPoise.
 6. Themethod of claim 1, wherein Brookfield viscosity of the softenedinterlayer is measured using a Brookfield rotational viscometer to beless than about 2,000 centiPoise.
 7. The method of claim 1, whereinBrookfield viscosity of the softened interlayer is measured using aBrookfield rotational viscometer to be less than about 1,500 centiPoise.8. The method of claim 1, wherein Brookfield viscosity of the softenedinterlayer is measured using a Brookfield rotational viscometer to beless than about 50 centiPoise to about 1,500 centiPoise.
 9. The methodof claim 1, wherein room temperature Brookfield viscosity of the firstsolidified interlayer is measured using a Brookfield rotationalviscometer to be greater than about 20,000 Poise.
 10. The method ofclaim 1, wherein room temperature Brookfield viscosity of the secondsolidified interlayer is measured using a Brookfield rotationalviscometer to be greater than about 20,000 Poise.
 11. The method ofclaim 1, wherein the polymeric film or laminate comprising the polymericfilm is at least partially pigmented and/or at least partiallymetallized.
 12. The method of claim 1, further comprising a step ofseparating the polymeric film, and any laminate of which it is a part,from the portion of the surface of the underlying article, leavingbehind a substantial portion of the second solidified interlayer on theunderlying article.
 13. The method of claim 12, further comprisingapplying a second polymeric film or second laminate comprising thesecond polymeric film to at least the portion of the surface of theunderlying article.
 14. The method of claim 1, wherein the articlecomprises a motorized vehicle.
 15. An article prepared according to themethod of claim 1, wherein the article comprises the following insequence: the polymeric film or laminate comprising the polymeric filmoutwardly exposed on the article; the second solidified interlayer; andthe underlying surface of the article.
 16. The article of claim 15,wherein the second solidified interlayer has a room temperatureBrookfield viscosity measured using a Brookfield rotational viscometerof greater than about 20,000 centiPoise.
 17. The article of claim 15,wherein the polymeric film is outwardly exposed on the article.
 18. Thearticle of claim 15, wherein the second solidified interlayer exhibits apeak loss factor of less than about 1.0.
 19. The article of claim 15,wherein the article comprises a motorized vehicle.
 20. An articleprepared according to the method of claim 13, wherein the articlecomprises the following in sequence: the second polymeric film or secondlaminate comprising the second polymeric film outwardly exposed on thearticle; the second solidified interlayer; and the underlying surface ofthe article.
 21. The method of claim 1, wherein there is a lack ofcovalent crosslinking between the first solidified interlayer and thepolymeric film or the laminate comprising the polymeric film of thepolymeric film assembly.
 22. The method of claim 1, wherein the firstsolidified interlayer exhibits a peak loss factor of less than about1.0.
 23. The method of claim 1, wherein the second solidified interlayerexhibits a peak loss factor of less than about 1.0.
 24. The method ofclaim 1, wherein only a portion of the solidified interlayer becomessoftened, and wherein the portion of the solidified interlayer incontact with the heated surface becomes softened.
 25. An articleprepared according to a method comprising steps of: providing apolymeric film or a laminate comprising the polymeric film; applying afirst solidified interlayer to a surface of the polymeric film or asurface of the laminate comprising the polymeric film to form apolymeric film assembly to be contacted with a portion of a surface ofan article; heating at least a portion of the surface of the article toform a heated surface; applying the polymeric film assembly to at leasta portion of the heated surface of the article by contacting the firstsolidified interlayer to the portion of the heated surface of thearticle such that at least a portion of the first solidified interlayerbecomes a softened interlayer positioned between the polymeric film andthe portion of the heated surface of the article; and converting thesoftened interlayer to a second solidified interlayer, which secondsolidified interlayer may be in a different form than or same form asthe first solidified interlayer initially provided, for adherence of thepolymeric film to at least the portion of the surface of the article,wherein Brookfield viscosity of the softened interlayer is measuredusing a Brookfield rotational viscometer to be less than about 10,000centiPoise, and wherein the article comprises the following in sequence:the polymeric film or laminate comprising the polymeric film outwardlyexposed on the article; the second solidified interlayer; and theunderlying surface of the article.
 26. The article of claim 25, whereinthe second solidified interlayer has a room temperature Brookfieldviscosity of greater than about 20,000 centiPoise.
 27. The article ofclaim 25, wherein the polymeric film is outwardly exposed on thearticle.
 28. The article of claim 25, wherein the second solidifiedinterlayer exhibits a peak loss factor of less than about 1.0.
 29. Thearticle of claim 25, wherein the article comprises a motorized vehicle.